Post reacted oligomers

ABSTRACT

This invention relates to novel oligomers of 1-alkenes and derivatives of acrylic acids, to methods of making the oligomers, and to compositions which comprise the oligomers.

This application is a divisional application of our earlier copendingapplication, Ser. No. 180,142, filed Sept. 13, 1971, and entitled"Copolymers of 1-Alkenes and Acrylic Acid Derivatives and Method ofMaking Same" now U.S. Pat. No. 3,968,148.

BACKGROUND OF THE INVENTION

The known techniques for preparing 1-alkene containing copolymers yieldproducts which have a wide molecular weight diversity and an extremecompositional heterogeneity. While the copolymers formed may displaysome beneficial properties, the overall effect of using a given amountof the polymer will be diminished by that part of the product having amolecular weight or composition which possesses detrimental ornon-useful qualtities. Thus, in order to produce a polymer in which thegood qualities are concentrated so that less of the polymer need be usedto accomplish a desired effect, it would be desirable to employ apolymerization technique which would allow for such control of polymermolecular weight and composition so that most of the polymeric materialproduced would have the beneficial qualities sought.

The prior art discloses a series of amide-containing copolymers whichare disclosed as useful as additives to oil, to wit, Bondi 2,800,452(filed July 1954), and Newey 2,912,416 (also filed July 1954). They donot, however, teach or suggest the presently disclosed 1-alkenesalkylacrylates higher alkyl acrylate oligomers, which have superior sludgedispersant properties.

The '416 patent recites an amide-containing copolymer based oncomponents which cannot produce the presently taught oligomers.

Similarly, the '452 patent does not include the higher alkyl acrylatecomponents of the type contemplated for use in the presently taughtoligomers; rather, it intended to exclude long chain esters, which wehave discovered contribute significantly to the here-desiredoil-solubility and/or dispersancy of the resulting oligomer.

Indeed, it can fairly be said that the cited patents actually lead awayfrom using higher alkyl acrylates, in view of their statements that suchcomponents are undesirably hydrolytically unstable.

THE INVENTION

Accordingly, it is an object of the invention to provide a novel processfor making oligomers.

Another object of the invention is to provide novel oligomers andoligomeric products comprising these oligomers.

A further object of the invention is to provide novel oligomerscontaining 1-alkenes and higher alkyl derivatives of acrylic acids andhaving a narrow range of molecular weight and high compositionalhomogeneity.

Still another object of the invention is to provide novel additives forlubricating oils which are useful as low temperature and ashless sludgedispersants and detergents. These and other objects will be apparentfrom the specification and claims.

It has now been found that these and other objects may be accomplishedby oligomers which are produced by an oligomerization process whichcomprises the continuous addition of at least one derivative of anacrylic acid to a mixture of a free radical initiator and at least onealkene-1 having 4 to 32 carbon atoms or more, in which the addition iscarried out at such a rate that the substantially instantaneous moleratio in the reaction mixture of the derivative to the alkene-1 ismaintained relatively constant at from about 0.01 to about 0.20 duringthe addition. At a given reaction temperature and catalystconcentration, the molecular weight of the oligomer produced will bedirectly related to the mole ratio of the acrylic acid derivative(s) tothe alkene-1. Varying this mole ratio between 0.01 and 0.20 will giveoligomers having a degree of polymerization of about 4 to about 35.

When the resulting oligomeric products of the invention are added tolubricating oils, they show activity as low temperature sludgedispersants and as detergents. Since oligomers produced by the processof the invention have relatively uniform molecular weight andcomposition, the effect of a given amount of the oligomer as a sludgedispersant or detergent can be heightened by suitable control ofmolecular weight and composition.

One of the advantages of the invention is that the molecular weight ofthe oligomer can be controlled, to give a product having a molecularweight falling within a narrow range, by adjusting the rate of additionof the acrylic derivative, in order to maintain a specified mole ratioof acrylic derivative to alkene-1 in the reaction mixture.

In producing the compounds which are useful as additives to lubricatingoils, the oligomers of the invention may be post-reacted with alcohols,esters, or amines to form new oligomeric products. Among thepost-reactions which are especially useful are the reaction of an esterof an acrylic acid with an alcohol to give a new acrylic ester throughtransesterification or with an amine to give an acrylic amide throughaminolysis, the reaction of an acrylic acid with an alcohol to give anacrylic ester, and the reaction of an alkyl nitrile with anethylenediamine to give an imidazoline.

Furthermore, a third monomer co-oligomerizable with the acrylic acidderivative and the alkene-1 may be added prior to the addition process,either to the acrylic derivative or to the alkene-1, thus forming aco-oligomer of the acrylic derivative, alkene-1 and said third monomer.Both of the above variations in the polymerization process of theinvention are useful for introducing valuable modifications into theoligomers of the invention.

The novel oligomers of the invention are oligomers of:

a. about 10 to 90% by weight of a 1-alkene or a mixture of 1-alkenes;

b. about 1 to 45% by weight of a straight or branched chain alkylacrylate or methacrylate in which the alkyl group contains 8 to 34carbon atoms, and;

c. 1 to about 35% by weight of an acrylic acid, ester or nitrile, or anamide or an amino derivative of an acrylic acid, or a mixture of suchacids, esters, nitriles, and amido and amino derivatives.

The first component of the oligomers of the invention is an olefin ofthe following Formula I: ##STR1## wherein R₁ is alkyl, and R₂ is H oralkyl.

Any polymerizable terminal olefin having 4 to 32 carbon atoms or morewhich will oligomerize with one of the acrylic acid derivatives can beused in the oligomerization process of the invention. Mixtures of suchalkenes can also be used.

Among the purposes of the alkene-1 are the following: to confer a highdegree of oil-solubility upon the oligomer, as well as close controlover the molecular weight. Examples of such oligomerizable olefinsdesirable for this purpose include: butene-1, pentene-1, hexene-1,heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1,tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1,octadecene-1, nonoadecene-1, eicosene-1, heneicosene-1, docosene-1,tricosene-1, tetradosene-1, pentacosene-1, hexacosene-1, heptacosene-1,octacosene-1, nonacosene-1, triacontene-1, hentriacontene-1,dotriacontene-1, and the like. Also useful are branched-chain alkenessuch as vinylcyclohexane, 3,3-dimethylbutene-1, 3-methylbutene-1,diisobutylene 4-methylpentene-1, and the like.

Likewise useful in this invention are alkene-1's having 10 to 32 carbonatoms, derived from the polymerization of ethylene, propylene, ormixtures thereof, which in turn are commercially provided fromhydrocracked stocks.

The second component of the oligomers of the invention is an acrylicester of the following formula II: ##STR2## where X is hydrogen ormethyl, and R is a straight or branched chain alkyl group having 8 to 34carbon atoms.

Mixtures of the compounds of formula II can also be used. Examples ofsuch compounds include: 2-ethylhexyl acrylate, isodecyl acrylate, decylacrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate,tetradecyl acrylate, pentadecyl acrylate, dodecyl-pentadecyl acrylate,hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate,cetylstearyl acrylate, oleyl acrylate, nonadecyl acrylate, eicosylacrylate, cetyl-eicosyl acrylate, stearyl-eicosyl acrylate, docosylacrylate, eicosyl-tetratriacontyl acrylate, and the like.

The third component of the oligomers of the invention is a compound ofthe following formula III: ##STR3## wherein R₁ may be H, CO₂ H or CO₂ R₄(R₄ is an alkyl group having 1 to 4 carbon atoms);

R₂ is (CH₂) X, wherein n is an integer ranging in value from 0 to 8, and

R₃ is hydrogen or methyl.

X may be halogen, -CO₂ H, -C.tbd. N, -CO₂ R₅ (R₅ may be any alkyl grouphaving 1 to 4 carbon atoms or it may be a polar moiety containing etheror sulfide or sulfinyl or hydroxyl or amine or amide groups orcombinations thereof and the like, (containing as many as 12 carbonatoms), or ##STR4## (Y is one of -NZ'Z", -O(CH₂)_(n) NZ'Z", .tbd.-O(CH₂)n CONZ'Z", -NHNZ'N" or -N^(-N) ^(+Z) ₃ " wherein n is a wholepositive integer from 1 to 12, Z' is hydrogen or an alkyl group straightor

branched of 1 to 20 carbon atoms,

Z" is hydrogen or an alkyl group of 1 to 20 carbon atoms

Z'" is an alkyl group of 1 to 4 carbon atoms, and

Z' and Z" can be taken together to form an azacylcoalkyl ring, anazacycloalkanone ring, a carbalkoxyazacycloalkanone ring, anoxaazacycloalkyl ring, an oxaazacycloalkanone ring or adiazacycloalkanone ring);

X may also be N-pyrrolidinyl and the like;

R₁ and R₂ together may be an anhydride group.

Among the compounds of formula III are acrylic acid, methacrylic acidsor derivatives thereof. Also included are suitably substitutedpolymerizable olefins which may be used to introduce into the oligomerfunctional groups to be subsequently transformed into dispersant sitesby reaction with amines and polyamines, esters, alcohols andaminoalcohols, or which may be derivatized with these compounds.

Examples of such substituted oligomerizable olefins include:4-chlorobutene-1, 4-pentenonitrile, 4-pentenoic acid, methyl4-pentenoate, ethyl 4-pentenoate, 5-hexenoic acid, 6-bromohexene-1,10-undecenoic acid, methyl 10-undecenoate, and ethyl 10-undecenoate, and4-pentenamides.

Mixtures of the compounds of Formula III may also be used. Examples ofsuch compounds include: acrylic acid, methacrylic acid, methyl acrylate,methyl methacrylate, methyl chloracrylate, ethyl acrylate, propylacrylate, n-butyl acrylate, acrylonitrile, 1-(methacryloxyethyl)-2-pyrrolidinone,1-(methacryloxyethoxyethyl)-2-pyrrolidinone, and the like.

Other examples are methylthioalkyl acrylate (alkylene group is C₁₋₉ ),ethylthioalkyl acrylate (alkylene group is C₁₋₈ ), alkylthioethylacrylate (alkyl group is C₁₋₈ ) and alkylsulfinylalkyl acrylates, inwhich the alkyl and alkylene groups together contain no more than tencarbon atoms, alkylthiopolyethoxyethyl acrylates containing one to fouroxyethylene groups, alkylthiopolypropyloxypropyl acrylates containingone to three oxypropylene groups, alkylsulfinylpolyethoxyethyl acrylatescontaining one to four oxyethylene groups,alkylsulfinylpolypropyloxypropyl acrylates containing one to threeoxypropylene groups (in each of the foregoing, the total number ofcarbon atoms of R₅ group is no more than ten), and the like.

Other examples of such derivatives include methacrylamide, acrylamide,N-methylacrylamide, N-ethylacrylamide, N-ethylacrylamide,N-butanolacrylamide, 2-(N-morpholino) ethyl acrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, N-t-butylacrylamide,N,N-di-n-butylacrylamide, N-(2-acryloxyethyl)-morpholinone-2-,N-(2-methacryloxyethyl)-morpholinone-2,N-(2-methacryloxyethyl)-5-carbo-n-butoxypiperidinone-2, 2-(N,Ndimethylamino) ethyl acrylate, 3-(N,N-dimethylamino) propyl acrylate,2-(N-t-butylamino) ethyl acrylate, 2-(N,N-dimethyl-amino) ethylmethacrylate, and 3-(N,N-dimethylamino)propyl methacrylate.

Two processes can be used in producing the oligomers of the invention.The first process comprises the continuous addition of at least onecompound of Formula I and II, to at least one compound of Formula IIIthat is already a dispersant monomer.

The addition is carried out at such a rate that the substantiallyinstantaneous mole ratio in the reaction mixture of compounds ofFormulas II and III to compounds of Formula I is maintained relativelyconstant at from about 0.01 to about 0.20 during the addition. A freeradical initiator is mixed with the Formula II compound, or Formula Icompound, or both, prior to the addition.

In the second process for producing the oligomer of the invention, anoligomer produced by the continuous addition of at least one compound ofFormulas II and III to at least one compound of Formula I, by a processsimilar to that described above, is post-reacted with an alcohol or anamine. Thus, when an acrylic acid or an acrylic ester is used as astarting monomer (that is, when R₁ is H and R₂ is -CO₂ H or -CO₂ R₄ inFormula III,) or when a substituted 1-olefin bearing an acid or estergroup is employed, the acid groups or the ester groups in the oligomercan be post-reacted with an alcohol or an amine having the formula HZ'";wherein Z'" is as defined in Formula III, or these groups can beneutralized or hydrolyzed with a base to form a salt of an acrylic acid.The relative amounts of the reactants can be chosen so that any desiredpercentage of the acid or ester groups can be converted to the desiredderivative.

Among the alcohols and amines which may be post-reacted with the acid orester groups in the oligomer are N-hydroxyethylmorpholinone-2,N-hydroxyethylpyrrlidone, N,N-dimethylaminoethylamine,5-aminopentylimidazoline, diethylenetriamine, aminoethylethylene urea,2-(2-aminoethyl)-aminoethanol, triethylenetramine,tetraethylenepentamine and N,N-dimethylaminopropylamine.

Besides these useful post-reactions we have found the reaction ofmultifunctional alcohols and amines with carboxylic acid groups presentin oligomers (to form esters, or amides or amine salts) to be a mosteffective way of introducing into the oligomers polar groups withdetergents, dispersant and/or anti-oxidant activity. The carboxylic acidgroups may be provided, for example, by the use of acrylic acid,4-pentenoic acid or 10-undecenoic acid as monomers.

Such alcohols and amines include ethylene glycol, diethylene glycol,triethylene glycol, glycerol, sorbitol, erythritol, trimethylene glycol,pentaerythritol, C₄₋₁₂ -alkyl glucosides, alkylthioalkanols andalkylsulfinylalkanols, where the alkyl and alkylene groups have one to12 carbons, 2,2'-thiodiethanol, 2,2'-sulfinyldiethanol, diethanolamine,triethanolamine, N-methyldiethanolamine, diglycolamine,N-methylformamide, glucosylamine, N-(B-hydroxyethyl)-morpholine,N-(B-hydroxyethyl)-morpholinone, 2-(2-aminoethylamino)-ethanol,N-(2-hydroxyethyl)-piperazine, 1-(B-hydroxyethyl)-2-pyrrolidinone,)-(hydroxyethoxyethyl)-2-pyrrolidinone, N,N-dimethylaminopropylamine,N-(2-aminoethyl)-ethyleneurea, N-(2-aminoethyl)-piperazine, calciumN-methyltaurate, ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Also, oligomeric carboxylic acids or their methyl or ethyl esters,having been post-reacted with diethylene triamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, etc., may be furtherreacted with one to five equivalents of methyl or ethyl formate, methylor ethyl acetate, ethylene oxide or propylene oxide, phosphoruspentasulfide, carbon disulfide, acrylo-or acetonitrile givingcorresponding formamides, acetamides, hydroxyethyl or hydroxypropyl,thiophosphoramide, thiocarbamate 2-cyanoethyl or imidazolinederivatives.

Any suitable catalyst may be used in the production of the copolymers ofthe invention. Among the preferred catalysts are peroxide catalysts,such as, for example, benzoyl peroxide, lauroyl peroxide, tertiary butylhydroperoxide, cumene hydroperoxide, 2,2-bis-(tertiarybutylperoxy)-butane, di-(tertiary butyl) peroxide tertiary butylperpelargonate, tertiary-butyl perbenzoate, hydrogen peroxide, andpercarbonates, peracetic acid, and the like. The amount of catalystwhich is added will vary, depending on the monomers employed as startingmaterials, reaction temperature, degree of polymerization desired, etc.,but generally the catalyst will be present at about 0.01 to 10% byweight of the material being polymerized, and preferably will be presentat about 0.1 to 1.0 percent by weight.

The temperature at which the oligomerization reaction is run can also bevaried over a broad range, and any temperature which will not impair theoligomerization can be selected. A preferred reaction temperature rangeis from about 100° C. to 200° C. While the choice of catalyst andreaction temperature may be used to exert some control over themolecular weight of the oligomers produced according to the invention,the major factor which determines the copolymer molecular weight is themole ratio of the acrylic acid derivative to the alkene-1, as describedabove.

In a preferred embodiment of the invention, the alkene-1 mixture and theacrylic acid derivatives will contain an alkyl chain of sufficientaverage length to impart oil-solubility to the oligomer. Among themonomers which are particularly useful in making oil-soluble oligomerare those having alkyl chains averaging 8 atoms or more, such astetradecene-1, n-dodecyl acrylate, and the like.

When the oligomeric products of the invention are added to lubricatingoils, they show activity as low temperature sludge dispersants and asdetergents. Since oligomers produced by the process of the inventionhave relatively uniform molecular weight and composition, the effect ofa given amount of the polymer as a sludge dispersant or detergent can beheightened by suitable control of molecular weight and composition.

One of the advantages of the invention is that the molecular weight ofthe oligomer can be controlled, to give a product having a molecularweight falling within a narrow range of distribution, by adjusting therate of addition of the acrylic derivative in order to maintain aspecified mole ratio of acrylic derivative to alkene-1 in the reactionmixture.

The following working examples illustrate systheses within the teachingof the present invention which may be employed in formulating thecompositions of the invention but are not considered limiting theinvention described heretofore.

EXAMPLE I Preparation of Oligomer: HD/DPA/AA/58.3/21.1/20/6

Into a 12-liter, 3-necked, round-bottom flask fitted with a motor-drivenC-stirrer, thermometer, reflux condenser and a 1000-ml. graduateddropping addition funnel is added 6207 g. (27.66 moles) of 1-hexadecene(HD) from Gulf Oil Corporation. The alkene is heated with stirring in anitrogen atmosphere to 132° and 7.30 g. (0.0319 mole) of 85% t-butylperbenzoate in xylene is added rapidly. A total of 497.7 g. (2.28 moles)of dodecyl-pentadecyl acrylate (DPA), 694.0 g. (9.63 moles) of acrylicacid (AA), and 4.44 g. (0.0194 moles) of 85% t-butyl perbenzoate isblended and charged to the dropping addition funnel; and addition ofacrylate/acrylic acid is carried out at a constant rate for 6.38 hours.The pot temperature is maintained at 132°-135° with moderate stirringfor 16 hours. The temperature is then raised to 192°, and unreactedmonomers are distilled under gradually reduced pressure to 1 mm. Hg.After 45 minutes at 192°/1 mm. Hg. the residue is cooled to 130° andweighed. After a sample had been removed for analysis, the remainingoligomer was diluted to a 52.0% solution with 100 neutral oil in orderto confer acceptable fluidity upon the product.

In a typical preparation, the amount of oligomer produced was 3001.5 g.(a 40.0% yield); it was found to have the compositionHD/DPA/AA/58.3/21.1/20.6 and a number-average molecular weight of 3200 ±10.

EXAMPLE IIA Preparation of the Oligomer: TD/DPA/AA//49.7/27.8/22.5

A 12-liter, 3-necked, round-bottom flask is charged with 5265 g. (26.8moles) of commercial tetradecene (92-93 % 1-tetradecene) and is thenfitted with a motor-driven Trubore C-stirrer, a candlestick adapterholding a thermometer and a 1-liter graduated dropping addition funnel,and a reflux condenser. The alkene is heated with stirring in anatmosphere of nitrogen to 132° C. A total of 6.20 g. of t-butylperbenzoate is added directly and five minutes later the continuousaddition of a solution of 1310 g. (5.00 moles) of dodecylpentadecylacrylate, 1035 g. (14.36 moles) of acrylic acid and 8.28 g. of t-butylperbenzoate is begun via the dropping addition funnel. With the reactiontemperature maintained at 132° -133°, the addition of acrylate solutionis completed in 4.75 hours; the product mixture is held at 132° (withstirring) for 16 hours. The temperature is then raised to 192° andunreacted monomers are distilled under gradually reduced pressure to 1mm. Hg. pressure. After 45 minutes at 192°/1 mm. Hg., the residue iscooled to 135° and weighed. After a sample of oligomer has been removedfor analysis, the remainder is diluted to 55% with 100 neutral oil togive a product with acceptable fluidity at room temperature.

In a typical preparation, the weight of oligomer produced was 4458 g. (a58.6% yield); it was found to have the compositionTD/DPA/AA//49.7/27.8/22.5 and a number-average molecular weight of 4240± 10, and diluted to a 52.0% solution with 100 neutral oil.

EXAMPLE IIB The Esterification of TD/DPA/AA//49.7/27.8/22.5; (M_(n) =4240 ± 10) with 2,2'-Sulfinyldiethanol

To a 2-liter, 3-necked round-bottom flask fitted with a motor-drivenC-stirrer, thermometer and a Dean-Stark trap connected to an Allihncondenser, are added 477.3 g. (0.8027 equiv., based on AA) of a 52.0%solution of the TD/DPA/AA oligomer of Ex. IIA in 100 neutral oil, 138.2g. (1.00 mole) of 2,2'-sulfinyldiethanol and 400 ml. of xylene. Themixture is heated under gentle reflux (152°-153°) with moderate stirringfor 6 hours, with water removed as it formed.

The product mixture is cooled to 105° and diluted with 272.2 g. of 100neutral oil. Xylene is removed by strip-distillation to 150°/2 mm. Hg.The product and unreacted 2,2'-sulfinyldiethanol are partitioned betweenhexane and 16% aqueous magnesium sulfate solution. Water is removed fromthe solution of product by azeotropic distillation and hexane is removedby strip-distillation to 135°/2 mm. Hg. Analysis of a typical productindicated that the extent of esterification was 37%.

A reaction product of the above ester and 2,2'-sulfinyldiethanol, inwhich 43% esterification was achieved, attained a sludge rating of 37.2(50.0 = clean), and a varnish rating of 33.6 (50.0 = clean) in the MSSequence V-B test after 192 hours.

EXAMPLE III The preparation of HD/DPA/AA//59.8/24.0/16.2

To a 12-liter, 3-necked, round-bottom flask fitted with a motor-drivenC-stirrer, thermometer, reflux condenser and two graduated droppingaddition funnels is added 3250.0 g. (14.48 moles) of 1-hexadecene. Thealkene is heated with stirring in a nitrogen atmosphere to 164° and amixture of 14.9 g. (0.057 mole) of dodecyl-pentadecyl acrylate, 9.1 g.(0.13 mole) of acrylic acid and 4.5 g. (0.022 mole) of dodecyl mercaptanis added rapidly. To one addition funnel is charged a mixture of 445.0g. (1.70 moles) of dodecylpentadecyl acrylate and 286.0 g. (3.97 moles)of acrylic acid, and to the other addition funnel is added a 400.0 g.(1.78 moles) of 1-hexadecene and 7.6 g. (0.033 mole) of 85% t-butylperbenzoate in xylene. The contents of each addition funnel are addedsimutaneously at a constant rate over 7.54 hours with the pottemperature maintained at 160°-164°.

Upon completion of addition of acrylate/acrylic acid and solution ofinitiator the reaction mixture is allowed to cool with stirring to 132°overnight (16 hours). The temperature is then raised to 192° andunreacted monomers are distilled under gradually reduced pressure to 1mm. Hg. After 45 minutes at 192°/1 mm. Hg. the residue is cooled to 135°and diluted to a 54.9% solution with 100 neutral oil.

In a typical preparation, the weight of oligomer produced was 1728.3 g.(a 39.2% yield). It was found to have the compositionHD/DPA/AA//59.8/24.0/16.2 and a number-average molecular weight of 2030± 20.

EXAMPLE IV Synthesis of the Oligomer: HD/DPA/MU//22.5/58.2/19.3

Into a 12-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux condenser and 1-liter graduateddropping addition funnel are charged 2074.2 g. (9.242 moles) of1-hexadecene and 1319.9 g. (6.656 moles) of methyl 10-undecenoate (MU).The alkene mixture is heated with stirring to 132° in a nitrogenatmosphere and 5.0 g. (0.022 mole) of 85% t-butyl perbenzoate in xyleneis added. A total of 1972.0 g. (7.527 moles) of dodecyl-pentadecylacrylate and 7.0 g. (0.031 mole) of 85% t-butyl perbenzoate are chargedto the dropping addition funnel; and addition of acrylate is carried outat a constant rate over 6.13 hours with the pot temperature maintainedat 132°-135°.

Upon completion of addition of acrylate, heating is continued at132°-134° with moderate stirring for 16 hours. The pot temperature isthen raised to 193° and unreacted monomers are distilled under graduallyreduced pressure to 2 mm. Hg. After 45 minutes at 193°/2 mm. Hg. theresidue is cooled to room temperature in a nitrogen atmosphere.

In a typical preparation, the weight of product was 3121.9 g. (a 58.2%yield). The oligomer was found to have the compositionHD/DPA/MU//22.5/58.2/19.3 with a number-average molecular weight of 3020± 15.

EXAMPLE V Synthesis of the Oligomer: HD/DPA/MP//27.9/62.0/10.1

Into a 12-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux condenser and 1-liter graduateddropping addition funnel are charged 2468.8 g. (11.00 moles) of1-hexadecene and 1009.3 g. (8.842 moles) of methyl 4-pentenoate (MP).The alkene mixture is heated with stirring continued 132°, in a nitrogenatmosphere, and 5.11 g. (0.0224 mole) of 85% t-butyl perbenzoate inxylene is added. A total of 2206.0 g. (8.420 moles) ofdodecyl-pentadecyl acrylate and 7.79 g. (0.0341 mole) of 85% t-butylperbenzoate are charged to the dropping addition funnel; and addition ofacrylate is carried out at a constant rate over 8.25 hours with the pottemperature maintained at 132°-134°. Upon completion of addition ofacrylate, heating is containued at 132°-134° with moderate stirring for15 hours. The pot temperature is then raised to 192° and unreactedmonomers are distilled under gradually reduced pressure to 1 mm. Hg.After 45 minutes at 192°/1 mm. Hg. the residue is cooled to roomtemperature in a nitrogen atmosphere.

In a typical preparation, the weight of product was 3556.7 g. (a 62.6%yield). The oligomer was found to have the compositionHD/DPA/MP//27.9/62.0/10.1 with a number-average molecular weight of 2875± 75.

EXAMPLE VI The Reaction of the Oligomer of Example V withDiethylenetriamine

To a 2-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer and reflux-distillation head are added400.0 g. (0.347 equiv., based on MP) of the oligomer of Ex. V and 62.0g. (0.601 mole) of technical-grade diethylenetriamine. The reactionmixture is heated with moderate stirring at 150°-155° for 6 hours in anitrogen atmosphere and methanol is removed as formed. The productmixture is diluted with 400.0 g. of 100 neutral oil and unreacted amineis strip-distilled at 155° with the pressure gradually reduced to 3 mm.Hg.

The product is cooled to room temperature in an atmosphere of nitrogen.In a typical preparation, a total of 802 g. of product, containing 1.52%nitrogen, was recovered. Analytical data indicated that 73.9% of thecarbomethoxy groups from MP had been amidated.

This material attained a sludge rating of 35.0 (50.0 = clean) and avarnish rating of 37.8 (50.0 = clean) in the MS Sequence V-B test (seeASTM Special Technical Publication No. 315-D) test after 192 hours.Under similar test conditions OLOA 1200 (a polybutane-based succinimide)a commercial product marketed by Socal, Oronite Division, achieved asludge rating of 35.1 and a varnish rating of 31.2.

EXAMPLE VII The Synthesis of the Oligomer: HD/DPA/MA//52.1/39.7/8.2

To a 2-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux condenser, 125-ml. graduateddropping addition funnel and a 250 ml. graduated dropping additionfunnel is added 589.6 g. (2.627 moles) of 1-hexadecene. The alkene isheated in a nitrogen atmosphere at 185° with moderate stirring. A totalof 1.615 g. (0.0106 mole) of cumene hydroperoxide in 6.01 g. (0.022mole) of 1-hexadecene is added rapidly. Seventeen minutes later thesimultaneous but separate additions of a solution of 245.0 g. (0.935mole) of dodecyl-pentadecyl acrylate and 65.3 g. (0.763 mole) of methylacrylate (MA) and a solution of 1.256 g. (0.00825 mole) of cumenehydroperoxide in 25.0 g. (0.111 mole) of 1-hexadecene are begun.

The continuous additions of monomers and initiator are carried out at aconstant rate, so that after 7.06 hours the addition of acrylatemonomers is complete, while that of initiator is 97% complete. Theremaining initiator is added rapidly and the reaction mixture is allowedto cool to 132° over the space of 16 hours with moderate stirring. Theproduct mixture is heated at 190° for 1.5 hours with moderate stirringin a nitrogen atmosphere and then unreacted monomers are removed bystrip-distillation at 190° with the pressure gradually reduced to 3.5mm. Hg. The residue is then cooled to 60° in a nitrogen atmosphere andclarified by filtration.

In a typical preparation, the weight of product was 608.8 g. (a 65.4%yield); the oligomer was found to have the compositionHD/DPA//MA//52.1/39.7/8.2 with a number-average molecular weight of 1625± 10.

EXAMPLE VIII The Reaction of the Oligomer: HD/DPA/MA//51.8/38.1/10.1with Triethylenetetramine

To a 3-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer and reflux-distillation head are added350.0 g. (0.4102 equiv., based on MA) of the oligomer and 73.2 g. (0.501mole) of triethylenetetramine. The mixture is heated at 140° withmoderate stirring in a nitrogen atmosphere for 8 hours. It is thencooled to 120° and diluted with 350.0 g. of 100 neutral oil, 300 ml. oftoluene and 300 ml. of isobutyl alcohol. A total of 100.0 g. (0.350equiv. H⁺) of Amberlyst 15 resin beads is added and the mixture isstirred slowly overnight at ambient temperature. The mixture is thenstirred in a nitrogen atmosphere at 85° for 1 hour and is cooled andfiltered. Solvents and traces of unsequestered triethylenetetramine areremoved by strip-distillation to 125° with the pressure graduallyreduced to 1.5 mm. Hg. The product is cooled in an atmosphere ofnitrogen.

In a typical preparation the product, which had a base number of 47.4and contained 1.68% nitrogen, was amidated at 48.7% of the carbomethoxygroups from MA and 3.6% of the carboalkoxy groups from DPA. Thismaterial attained a sludge rating of 36.2 (50.0 = clean) and a varnishrating of 32.1 (50.0 = clean) in the MS Sequence V-B test after 192hours. Under similar test conditions, OLOA-1200 a commercial product (apolybutene-based succinimide) marketed by Socal, Oronite Division,achieved a sludge rating of 35.1 and a varnish rating of 31.2.

EXAMPLE IX The Reaction of Ethyl Formate with the OligomerHD/DPA/MA//50.3/39.8/9.9 Previously Condensed with Triethylenetetramine

To a 2-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux-distillation head and 125 ml.dropping addition funnel is added 771.7 g. (0.486 equiv. of primaryamine) of the amidated oligomer. This material is the condensationproduct of the oligomer (HD/DPA/MA//50.3/39.8/9.9; M_(n) = 1745 ± 15)and triethylenetetramine, in which 45.4% of the carbomethoxy groups fromMA and 19.6% of the carboalkoxy groups from DPA had been amidated. Theoligomer is heated with moderate stirring to 88° in an atmosphere ofnitrogen, and 42.4 g. (0.572 mole) of ethyl formate is added dropwiseover the space of 10 minutes. Heating is continued at 88° for 2 hours.Volatile material is stripped at 90° with the pressure gradually reducedto 1 mm. Hg. The product is then cooled in an atmosphere of nitrogen. Ina typical preparation, a total of 0.432 equiv. of amine are formulated.

A formulated oil containing 1.20% of this product as the sludgedispersant showed 11% top-groove fill after 240 hours in the Caterpillar1-H test. The same oil lacking a dispersant showed 36% top-groove fillafter 240 hours.

EXAMPLE X The Synthesis of the Oligomer: HD/CEA/MA//48.7/41.7/9.6

To a 3-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux condenser, 125-ml. graduateddropping addition funnel and a 1-liter graduated dropping additionfunnel are added 901.3 g. (4.016 moles) of 1-hexadecene. The alkene isheated in a nitrogen atmosphere at 185° with moderate stirring. A totalof 0.90 g. (0.0059 mole) of cumene hydroperoxide in 10.0 g. of tridecaneis added rapidly. Ten minutes later the simultaneous but separateadditions of a solution of 280.0 g. (0.8578 mole) of cetyl-eicosylacrylate (CEA) and 77.4 g. (0.899 mole) of methylacrylate and 2.5 gm. ofcumene hydroperoxide in 50.0 g. of tridecane are begun. The continuousadditions of monomers and initiator proceeds at a constant rate and iscompleted after 6.93 hours.

The reaction mixture is allowed to cool to 132° over the space of 17hours with moderate stirring. The product mixture is then heated to 192°and unreacted monomers are removed by strip-distillation at 193° withthe pressure gradually reduced to 3 mm Hg. The residue is cooled to roomtemperature in an atmosphere of nitrogen and is clarified by filtration.

In a typical preparation, the weight of product was 662.9 g. (a 52.7%yield); the oligomer was found to have the compositionHD/CEA/MA//48.7/41.7/9.6 with a number-average molecular weight of 1425± 25.

EXAMPLE XI The Synthesis of the Oligomer: OD/DPA/MA//65.0/14.3/20.7

To a 5-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, reflux condenser, 125 ml. graduateddropping addition funnel and a 1-liter graduated dropping additionfunnel is added 2424.9 g. (9.604 moles) of 1-octadecene. The alkene isheated at 185° with moderate stirring in a nitrogen atmosphere. A totalof 0.8169 g. (0.00537 mole) of cumene hydroperoxide in 25.0 g. (0.099mole) of 1-octadecene is added rapidly. Seventeen minutes later thesimultaneous but separate additions of a solution of 262.0 g. (1.00mole) of dodecylpentadecyl acrylate, and 416.6 g. (4.737 moles) ofmethyl acrylate, and a solution of 4.5322 g. (0.02978 mole) of cumenehydroperoxide in 75.0 g. (0.297 mole) of 1-octadecene are begun.

The continuous addition of monomers and initiator proceeds at a constantrate and after 7 hours the addition of acrylate monomers is complete,while that of initiator is 93.3% complete. The remaining initiator isadded rapidly and heating at 185° is continued for 1 hour. The reactionmixture is allowed to cool overnight (16 hours) to 130° with moderatestirring. Unreacted monomers are removed by strip-distillation at 210°with the pressure gradually reduced to 1 mm Hg. The residue is cooled toroom temperature in an atmosphere of nitrogen and is clarified byfiltration.

In a typical preparation, the weight of product was 1835.6 g. (a 57.3%yield); the oligomer was found to have the compositionOD/DPA/MA//65.0/14.3/20.7 with a number average molecular weight of 1660± 40.

EXAMPLE XII The Reaction of the Oligomer of Example XI withTriethylenetetramine

To a 3-liter, 4-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer and reflux-distillation head is added1660 g. (3.99 equiv., based on MA) of oligomer and 153.5 g. (1.05 mole)of triethylenetetramine. The mixture is heated at 130° with moderatestirring in an atmosphere of nitrogen for 8 hours, with methanoldistilled upon its formation. Unreacted amine and other volatilematerials are removed by vacuum strip-distillation to 155°/1 mm Hg. withintermittent sparging with nitrogen. The product is cooled in anatmosphere of nitrogen. In a typical preparation, a total of 1738 g. ofproduct, with a base number of 67.8 and a nitrogen content of 2.86% wasrecovered. Analytical data indicated that 20.7% of the carbomethoxygroups from MA and 7.7% of the carboalkoxy groups from DPA wereamidated.

A formulated oil containing 1.20% of the product as the sludgedispersant showed 3% top-groove fill after 409 hours in the Caterpillar1-H test. The same oil lacking a dispersant showed 36% top-groove fillafter only 240 hours.

EXAMPLE XIII The Reaction of Ethylene Oxide with the OligomerOD/DPA//MA/65.1/13.9/21.0 Previously Condensed with Triethylenetetramine

To a 2-liter, 4-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, gas inlet and reflux condenser(Dewar-type) cooled with acetone-Dry Ice are added 787.6 g. (0.365equiv. of primary amine) of the title amidated oligomer, 200 ml. ofisobutyl alcohol, 100 ml. of isopropyl alcohol and 5.0 ml. of water.This oligomer is the condensation product of the oligomerOD/DPA/MA//65.1/13.9/21.0 (M_(n) = 1610 ± 15) and thetriethylenetetramine, in which 21% of both the carbomethoxy groups fromMA and carbalkoxy groups from DPA have been amidated. The mixture isheated with vigorous stirring at 70° while 18.0 g (0.406 moles) ofethylene oxide is distilled into the flask over a 45-minute period.

After holding the product mixture at 70° for 15 minutes, solvents aredistilled at 100° with the pressure gradually reduced to 1 mm Hg.Quantitative reaction of ethylene oxide is observed.

A formulated oil containing 1.20% of the product as the sludgedispersant showed 6% top-groove fill after 240 hours in the Caterpillar1-H test. The same oil lacking a dispersant showed 36% top-groove fillafter 240 hours.

EXAMPLE XIV Reaction of the Oligomer OD/DPA/MA//64.9/14.1/21.0 withDiethylenetriamine

To a 2-liter, 4-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, stopper and reflux-distillation head arecharged 875.0 g. (2.13 equiv., based on MA) of the title oligomer and71.4 g. (0.691 mole) of diethylenetriamine The components are heatedwith moderate stirring for 8 hous at 140°-142° in an atmosphere ofnitrogen, with methanol distilled upon its formation. Upon expiration ofthe reaction time, unreacted amine and other volatile materials areremoved by vacuum strip-distillation to 140° C./1.5 mm Hg. pressure withintermittent sparging with nitrogen. The product is cooled in anatmosphere of nitrogen. A total of 898.7 g. of product, with a basenumber of 53.3 and a nitrogen content of 2.51%, are recovered.

In a typical preparation analytical data indicated that 23.9% of thecarbomethoxy groups from MA and 6.6% of the carboalkoxy groups from DPAhad been amidated.

A formulated oil containing 1.20% of the product as the sludgedispersant showed 20% top-groove fill after 480 hours in the Caterpiller1-H test. The same oil lacking a dispersant showed 36% top-groove fillafter only 240 hours.

EXAMPLE XV The Synthesis of the Oligomer: HD/DPA/MEOP//36.1/33.6/30.3

To a 2-liter, 3-necked, round-bottom flask fitted with a motor-drivenTrubore C-stirrer, thermometer, a reflux condenser, 125 ml. graduateddropping addition funnel and a 1-liter graduated dropping additionfunnel are added 584.5 g. (2.604 moles) of 1-hexadecene. The alkene isheated at 185° with moderate stirring in a nitrogen atmosphere. A totalof 1.615 g. (0.0106 mole) of cumene hydroperoxide in 15.6 g. (0.0696mole) of 1-hexadecene is added rapidly. Fifteen minutes later thesimultaneous but separate additions of solution of 245.0 g. (0.935 mole)of dodecyl-pentadecyl acrylate and 188.4 g (0.758 mole) of1-(methacryloxyethoxyethyl)-2-pyrrolidinone and a solution of 2.1164 g.(0.0139 mole) of cumene hydroperoxide in 20.5 g. (0.0917 mole) of1-hexadecene are begun. The continuous addition of monomers andinitiator proceeds at a constant rate. After 7.50 hours, the addition ofacrylate monomers is complete, while that of initiator is 94% complete.The remaining initiator solution is added rapidly and the reactionmixture is allowed to cool to 130°-132° over the space of 16 hours withmoderate stirring. The product mixture is heated at 190° for 1 hour in anitrogen atmosphere with moderate stirring and unreacted monomers areremoved by strip-distillation at 190° with the pressure graduallyreduced to 3 mm Hg. The residue is cooled to ambient temperature in anitrogen atmosphere and clarified by filtration.

In a typical preparation, the weight of product was 556.9 g. (a 52.8%yield). The oligomer, a cherry-red liquid, was found to have thecomposition HD/DPA/MEOP//36.1/33.6/30.3 with a number-average molcularweight of 1425 ± 25.

EXAMPLE XVI Cooligomerization of Tetradecene-1,Lauryl Acrylate andN-(B-Acryloxyethyl)-Morpholinone-2 (BAEM)

Into a tared 500 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer, nitrogen inlet tube, refluxcondenser and a 125 ml. pressure equalized graduated addition funnelwere weighted 110 g. of tetradecene-1 and 0.2 g. of dicumyl peroxide.After an initial deaeration period of approximately 20 minutes withnitrogen at room temperature, the variable transformer controlling aheating mantle is turned on high, and the temperature of the contents ofthe flask raised to 150° C. A dropwise addition of the contents of theaddition funnel consisting of a homogeneous solution of 84 g. of laurylacrylate, 6 g. of BAEM above and 0.8 g. of dicumyl peroxide is thenbegun at such a rate that the total addition time is approximately 3hours. The reaction mixture is kept at 150° C. with stirring and under anitrogen blanket overnight (15 hours).

After the flask is weighed (total weight yield); 201 g.), 183.6 g. ofthe reaction mixture are stripped under reduced pressure (up to about150° C. at 0.5-mm. Hg.) to give 96.2 g. of oligomer which corresponds toa weight yield of 52.4%. Analysis of the unstripped reaction mix byvapor phase chromatography and titration of the stripped oligomer usinga standard perchloric acid solution in acetic acid gives the followingfinal composition: Lauryl acrylate: tetradecene-1: BAEM 70.3:25.2:4.5 byweight. Kjeldahl nitrogen analysis gives a value of 0.39% Ncorresponding to 5.5% by weight of BAEM in the oligomer. Elementalanalysis:

    ______________________________________                                        C          H           O          N(Kj)                                       ______________________________________                                        76.18      12.23       10.85      0.39                                        ______________________________________                                    

EXAMPLE XVII Cooligomerization of Tetradecene-1, 2-Ethyl-hexyl Acrylateand N-Methacryloxyethyl-N-Methylformamide (MAMF)

Into a tared 500 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer, nitrogen inlet tube, refluxcondenser and a 125 ml. pressure equalized graduated addition funnel areweighed 110 g. of tetradecene-1 (Gulf). After deaerating with nitrogenfor about 20 minutes, the tetradecene is heated to 140 ± 5° C. using aheating mantle connected to a variable transformer. Using a graduatedone milliliter pipette, 0.33 ml. of a 70% solution of tertiary butylhydroperoxide (TBHP) are added and a dropwise addition of a solution of74 g. of 2-ethyl-hexyl acrylate, 16 g. of MAMF and 0.66 ml. of 70% TBHPis begun at such a rate that the addition is finished after about twohours. About 0.3 ml. of 70% cumene hydroperoxide (=0.1% by weight) areadded and the stirring continued at 135°-140° C. overnight undernitrogen.

Total weight recovered was 199.6 g. Analysis of the unstripped reactionmix by vapor phase chromatography showed no residual 2-ethylhexylacrylate, and oligomer yield of 62.3% and together with a Kjeldahlnitrogen (0.97%) determination on a stripped sample indicates anoligomer composition of 2-ethylhexyl acrylate:tetradecene-1:MAMF =60.7:28.3:11.8 by weight. A number average molecular weightdetermination by thermal tensimetry gave an average value of 2082.Elemental analysis:

    ______________________________________                                        C          H           O          N(Kj)                                       ______________________________________                                        73.97      11.27       13.79      0.97                                        ______________________________________                                    

EXAMPLE XVIII Cooligomerization of Tetradecene-1, Lauryl Acrylate and4-Pentenoic Acid

Into a tared 3000 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer, nitrogen inlet tube, refluxcondenser and a 500 ml. pressure equalized graduated addition funnel areweighed 520 g. of tetradecene-1 and 80 g. of 4-pentenoic acid.

Heating and sparging of the flask with Nitrogen are startedsimultaneously, after 10 minutes, with a temperature of 100° C. isreached, 1.0 ml. of tertiary butyl perbenzoate (TBPB) is added to theflask. When after an additional 10 minutes a temperature of 130° C. isreached, a slow addition of solution of 2.0 ml. of TBPB in 400 g. oflauryl acrylate is started at such a rate that the addition is finishedin 3 hours. The reaction mixture is stirred at 130° C. under nitrogenfor an additional 20 hours. The total weight obtained is 1000.5 g., ofwhich 952.5 g. are stripped under reduced pressure to give 360.0 g. ofdistillate and 592.5 g. of oligomer which corresponds to a yield of62.2% by weight. Analysis of an unstripped sample by vapor phasechromatography (VPC) indicates the following composition for theoligomer: lauryl acrylate: tetradecene-1: pentenoic acid = 64.2:30.2:5.6by weight; titration of acidity by a standard KOH solution inisopropanol gave a level of 4.8% pentenoic acid in the stripped sample.Since this number is not based on differences between starting andresidual concentrations as is the VPC results, it can be assumed to bemore accurate. The oligomer composition is therefore, lauryl acrylate:tetradecene-1:pentenoic acid = 64.7:30.5:4.8 by weight.

EXAMPLE XIX Cooligomerization of Tetradecene-1, 2-Ethylhexyl Acrylateand N-Vinyl pyrrolidone (NVP)

Into a tared 500 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer, nitrogen inlet tube, refluxcondenser and a 125 ml. pressure equalized graduated addition funnelwere weighted 110 g. of tetradecene -1. The flask is sparged withnitrogen at room temperature for about 40 minutes, then heated to 110°C. using a heating mantle controlled by a variable transformer. Asolution of 0.1 g. of benzoyl peroxide dissolved in the minimum amountof ethyl acetate is added and a dropwise addition of a solutionconsisting of 76 g. of 2-ethylhexyl acrylate, 14 g. of N-vinylpyrrolidone is begun. The reaction temperature is kept between 110° C.and 115° C. and the addition finished after 3.5 hours. After theaddition of 0.33 ml. of 70% tertiary butyl hydroperoxide, the reactionmixture is kept at 110° C. under nitrogen and with agitation for 15additional hours. A total of 206 g. of material is obtained (includingsome ethyl acetate). Vapor phase chromatography indicates a weight yieldof approximately 62.5% Kjeldahl nitrogen on a stripped sample is 1.23%by weight -- this together with the VPC analysis of the residualmonomers gives as a final oligomer composition: ethylhexyl acrylate:tetradecene:NVP = 61.9:28.4:9.7 by weight. The elemental analysis gavethe following results:

    ______________________________________                                        C          H           O          N(Kj)                                       ______________________________________                                        75.22      11.60       12.55      1.23                                        ______________________________________                                    

If the composition is calculated from the elemental analysis, theethylhexyl acrylate and tetradecene percentages change to 63.9% and26.4% respectively. A determination of the number average molecularweight by thermal tensimetry gave 4291 as the average of threemeasurements.

EXAMPLE XX Reaction of 2-(5-Aminopentyl) Imidazoline with a Cooligomerof Tetradecene-1, Lauryl Acrylate and Methyl-4-Pentenoate

Into a tared 500 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer, nitrogen inlet tube and a Barretttype moisture test receiver fitted with a reflux condenser, are placed250 g. of an oligomer of the composition laurylacrylate:tetradecene-methyl pentenoate = 66.9:17.4:15.7 by weight whichhas been prepared by the same technique as described under Ex. XVIII andstripped under reduced pressure to remove unreacted monomer. Enough2-(5-aminopentyl) imidazoline to equal one-half the moles concentrationof the methyl pentenoate present is added to the flask (26.8 g.). Thecontents of the flask are heated to 120°-125° C. and kept at thistemperature under nitrogen with stirring for about 20 hours. After thereaction mix had cooled slightly, it was poured into a 4-8 fold excessof cold, reagent grade methanol under thorough agitation. After a fewminutes, the stirring is stopped and after phase separation the methanollayer is removed, using a thin glass tube attached to a suction flaskwhich in turn is connected to a water-operated aspirator pump. To themethanol-swollen oligomeric material is added an excess of reagentgrade, cold methanol and the same wash cycle repeated. After a total of4-methanol wash cycles, the oligomeric material is transferred to arotating high vacuum type evaporator and stripped under reduced pressureto remove all traces of methanol. A Kjeldahl nitrogen determination gave1.72% of nitrogen for the final product which is equal to 6.35% byweight of the imidazoline and therefore indicates that the reactionyield was about 66%. The C = O stretching bands appearing in theinfrared scan of the final product taken as a film on a sodium chlorideplate are consistent with amide-formation.

EXAMPLE XXI Esterification of an Oligomer of Tetradecene-1, LaurylAcrylate and 4-Pentenoic Acid with N-(B-Hydroxyethyl)-Morpholinone-2

Into a tared 500 ml., three-neck, round bottom flask, equipped with anair motor-driven stirrer, thermometer and a Barrett type moisture testreceiver fitted with a reflux condenser, are placed 250 g. of theoligomer prepared in Ex. XVIII which had been stripped and thecomposition of which is: lauryl acrylate:tetradecene-1: pentenoic acid =64.7:30.5:4.8 by weight. Also added to the flask are 1.2 times the molarequivalent of pentenoic acid present ofN-(B-hydroxyethyl)-morpholinone-2(20.9 g.), and 54 g. of xylene in orderto facilitate the removal of the water produced. Using a heating mantlecontrolled by a variable transformer the contents of the flask areheated to 200° C. and kept at this temperature for about 20-22 hourswith agitation; approximately 2 ml. of water codistilled over duringthis time. The reaction mixture is stripped under reduced pressure andfiltered through a pressure filtration funnel. The Kjeldahl nitrogendetermination on the final oligomeric material gives a value of 0.61%which corresponds to 0.436 milliequivalents per gram; since theconcentration of the acid is 0.48 milliequivalents per gram, thereaction yield amounts to 0.436/0.48 × 100 = 91%.

We claim:
 1. An oligomer ofa. about 10 to about 90 weight percent of a1-alkene, or of a mixture of 1-alkenes, all having 4 to 32 carbon atoms;b. about 1 to about 35% of a compound or compounds having the formula:##EQU1## wherein X is hydrogen or a methyl group, and R is a straight orbranched chain alkyl group having 8 to 34 carbon atoms, and; c. 1 toabout 35% of a compound or compounds having the formula: ##EQU2##wherein R₂ is hydrogen or a methyl group, and R₃ is (CH₂ -)_(n) X,wherein n is an integer ranging in value from 0 to 8, and X is any alkylgroup having 1 to 4 carbon atoms,post-reacted with an amine of theformula Nh₂ (ch₂ ch₂ nh)_(m) H wherein m is 1 to 6.